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Bright Multicolor Bandgap Fluorescent Carbon Quantum
Communication
Dots for Electroluminescent Light-Emitting Diodes
Fanglong Yuan, Zhibin Wang, Xiaohong Li, Yunchao Li, Zhan’ao Tan,* Louzhen Fan,*
and Shihe Yang
The development of electroluminescent light-emitting diodes
(LEDs) has been the subject of intense academic research
for years, in anticipation for applications in back-lighting in
liquid-crystal displays (LCDs), full-color displays, and as next-
generation lighting sources for our daily life.[1–3] Colloidal semi-
conductor quantum dots (QDs), such as CdSe, CdTe, and PbTe,
have emerged as excellent candidates for the development of
display and lighting technology due to their unique and attrac-
tive characteristics such as bandgap emission, high quantum
yield (QY), and narrow emission bandwidths that are easily tun-
able by controlling the size of QDs during synthesis.[4–6] Great
progress has been made for the design and fabrication of high-
performance QD-based LEDs with simple device configurations
and high spectral purities that outperform those of LCDs and
organic LEDs (OLEDs).[7,8] However, severe toxic and detri-
mental effects to humans and the environment are still crucial
impediments to the use of Cd2+/Pb2+-based QDs as next-gener-
ation luminophores for future LEDs.[9,10]
The emerging quantum-sized (<10 nm) carbon dots (CDs)
appear to be an ideal alternative to Cd2+/Pb2+-based semicon-
ductor QDs in electroluminescent LEDs for their tunable
stable fluorescence emission, low cost, and especially for being
environment-friendly.[11–16] Therefore, it comes as no surprise
that great efforts have been made to improve the properties of
CDs for their potentially wide applications in electrolumines-
cent LEDs. Significantly, the QY of blue fluorescent CDs was
reported to be as high as 80%, which is comparable to the
best inorganic semiconductor QDs.[17,18] However, the obvious
excitation-dependent fluorescence of CDs is dominated by
surface defects or molecule states, which gives rise to funda-
mental limitations to the effectiveness of carrier injection for
electroluminescent LEDs applications.[19] To make up for it, the
F. L. Yuan, Prof. X. H. Li, Prof. Y. C. Li, Prof. L. Z. Fan
Department of Chemistry
Beijing Normal University
Beijing 100875, China
E-mail: lzfan@bnu.edu.cn
Z. B. Wang, Prof. Z. A. Tan
New and Renewable Energy of Beijing Key Laboratory
School of Renewable Energy
North China Electric Power University
Beijing 102206, China
E-mail: tanzhanao@ncepu.edu.cn
Prof. S. H. Yang
Department of Chemistry
The Hong Kong University of Science and Technology
Clear Water Bay
Kowloon, Hong Kong, China
DOI: 10.1002/adma.201604436
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well-developed polymer hole transport layer (HTL) commonly
used in optoelectronic devices has been used in CD-based elec-
troluminescent LEDs.[20–23] However, a clear physical mecha-
nism underlying the electroluminescence (EL) emission from
CDs in the device or the origin of the EL emission has not been
directly demonstrated due to the interference of the EL from
HTL. In addition, the performance of these LEDs such as the
maximum luminance (Lmax) and current efficiency (ηc) is still
too low. There is no doubt that the best approach for realizing
CDs-based electroluminescent LEDs is to achieve high-quality
bandgap fluorescent carbon quantum dots (BF-CQDs).
In this work, we report the first demonstration of bright
multicolor bandgap fluorescent CQDs (MCBF-CQDs) from
blue to red with a QY up to 75% for blue fluorescence. This
was achieved by the successful solvothermal synthesis of the
MCBF-CQDs by simply controlling the fusion and carboniza-
tion of citric acid (CA) and diaminonaphthalene (DAN) with a
unique amino-substituted rigid carbon skeleton structure. Sig-
nificantly, as-prepared MCBF-CQDs are nitrogen doped, highly
surface-passivated, and have a high degree of crystallinity. As
a direct benefit of the bandgap emission, the first example of
monochrome electroluminescent LEDs with stable emission
color from blue to red based on MCBF-CQDs directly used as
an active emission layer without HTL has been realized. The
LEDs show very stable and voltage-independent emission color.
The Lmax reached 136 cd m−2 for blue LEDs, which represents
the best performance for CQDs-based monochrome electro-
luminescent LEDs. Moreover, white LEDs (WLEDs) with a
Commission International d’Eclairage (CIE) color coordinate
at (0.30, 0.33) are also fabricated by using BF-CQDs blended
poly(N-vinyl carbazole) (PVK) as an emissive layer. The Lmax
and ηc reach about 2050 cd m−2 and 1.1 cd A−1, respectively,
even comparable to semiconductor QD-based LEDs.
The synthesis of MCBF-CQDs from blue to red (named B-,
G-, Y-, O-, and R-BF-CQDs, respectively), as shown in Figure 1a,
involved the mixing of CA with DAN (2,3-diaminonaphthalene
or 1,5-diaminonaphthalene) in an ethanol solution, followed by
solvothermal treatment at 200 °C with different reaction times or
adding appropriate amounts of concentrated sulfuric acid based
on the experimental design to yield redshifts in the photolumi-
nescence (PL) emission (further details can be found in Experi-
mental Section). The yield from this facile solvothermal strategy
for the fabrication of MCBF-CQDs is about 53%, which is suitable
for industrial-scale production. As-prepared MCBF-CQDs can be
dispersed within a variety of common solvents to form clear solu-
tions. The MCBF-CQDs ethanol solution displays a clear color
appearance under daylight (Figure 1b, left) and bright fluores-
cence colors from blue to red under UV light (excited at 365 nm,
Figure 1b, right), which is easily perceived with the naked eye.
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Figure 1. a) Preparation of MCBF-CQDs from blue to red by solvothermal
treatment of CA and DAN. b) Photographs of MCBF-CQDs under daylight
(left) and fluorescence images (right) under UV light (excited at 365 nm). the emission are bandgap emissions instead of surface-defect
The most distinctive feature of MCBF-CQDs that sets them
apart from other previously reported CDs is their specific
optical properties. The MCBF-CQDs show strong excitonic
absorption bands in the UV–vis absorption spectra (Figure 2a)
centered at about 350, 390, 415, 480, 500 nm for B-, G-, Y-, O-,
and R-BF-CQDs, respectively, which is similar to the absorption
characteristics of quantum-confined semiconductor QDs but
quite different from that of previous reported CDs within only
the UV region.[11–15,24] The fluorescence peaks of MCBF-CQDs
Figure 2. a) UV–vis absorption, b) normalized fluorescence, and c) time-resolved PL spectra
of B-BF-CQDs, G-BF-CQDs, Y-BF-CQDs, O-BF-CQDs, and R-BF-CQDs. Dependence of d) the
HOMO and LUMO energy levels with respect to the size of MCBF-CQDs.
Adv. Mater. 2017, 29, 1604436 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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(Figure 2b) are centered at about 430 (B-), 513 (G-), 535 (Y-),
Communication
565 (O-), and 604 nm (R-BF-CQDs), respectively. The red-
shifted fluorescence colors from blue to red are consistent
with the red-shifted excitonic absorption bands, implying the
band-edge nature of the optical transitions in MCBF-CQDs.
Notably, the overlap between excitonic absorption and emis-
sion spectra of MCBF-CQDs is quite small, leading to small
self-absorption, which is a benefit for efficient fluorescence
emission (Figure S1, Supporting Information). The PL of
MCBF-CQDs can be excited in a wide wavelength range and
the maximum emission peaks are well confined, nearly irre-
spective of excitation wavelength (Figure S2, Supporting Infor-
mation), indicating that the PL origin is markedly dissimilar
to that of the previous reported excitation-dependent emission
of CDs. The maximum excitation wavelength agrees well with
the corresponding excitonic absorption peak (Figure S3, Sup-
porting Information), suggesting that the emission is character-
ized by band-edge exciton-state decay rather than defect-state
decay.[25,26] The pH-independent emission peaks of MCBF-
CQDs (Figure S4, Supporting Information) further indicate that
states emissions. The bandgap transitions in MCBF-CQDs
were further confirmed by size-dependent optical properties
through transmission electron microscopy (TEM) and atomic
force microscope (AFM) characterizations. As shown in Figure S5
(Supporting Information), all of the five BF-CQDs show uni-
form and narrow distributed nanoparticles with average sizes
of about 1.95 (B-), 2.41 (G-), 3.78 (Y-), 4.90 (O-), and 6.68 nm
(R-BF-CQDs) with heights largely in the range of 1 to 2 nm
corresponding to ≈1–4 graphene layers (Figure S6, Supporting
Information), and their typical high-resolution TEM (HRTEM)
images (insets of Figure S5, Supporting Infor-
mation) further indicate that most of the BF-
CQDs exhibit uniform atomic arrangements
with high degree of crystallinity. The gradually
increased size of MCBF-CQDs is consistent
with the red-shifted PL wavelength and the
first excitonic absorption peak wavelength,
which clearly reveal the bandgap transitions
in MCBF-CQDs, which originates from the
quantum confinement effect (Figure S7,
Supporting Information).[27–30] Other evi-
dence for the bandgap emission properties
was obtained by time-resolved PL analysis
(Figure 2c), which determined monoexponen-
tial decay with relative long fluorescence life-
times of about 14.2, 12.2, 11.3, 8.8, and 6.8 ns
for B-, G-, Y-, O-, and R-BF-CQDs, respec-
tively. The monoexponential decay charac-
teristics indicate that the excitons are highly
stable and do not find nonradiative emission
channels within the MCBF-CQDs, which are
conducive to efficient fluorescence emission
and visibly different from reported CDs with
multi-exponential decay.[31] The QY of MCBF-
CQDs was determined to be 75%, 73%, 58%,
53%, and 12% for B-, G-, Y-, O-, and R-BF-
CQDs, respectively, and is the highest value
reported for BF-CQDs. The decreased degree
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of surface passivation of electron-donating amino groups at
Communi ation
edge sites may result in the gradually decreased QY of BF-
CQDs as the size of CQDs increased.
Bandgap energies of MCBF-CQDs were further calculated
using the equation Egopt = 1240/λedge, where λedge is the onset
c
value of the first excitonic absorption bands in the direction of
longer wavelengths. The calculated bandgap energies gradu-
ally decreased from 3.02 to 2.12 eV when the size of BF-CQDs
increased from 1.95 to 6.68 nm (Table S1, Supporting Informa-
tion), further demonstrating the obvious size-dependent prop-
erty of bandgap energies. Meanwhile, the decreased highest
occupied molecular orbital (HOMO) levels from 5.72 to 5.27 eV
determined by means of ultraviolet photoelectron spectroscopy
(UPS) (Figure S8, Supporting Information) and the increased
lowest unoccupied molecular orbital levels from 2.70 to 3.15 eV
(Table S1 of the Supporting Information and Figure 2d) directly
reveal the bandgap transitions in MCBF-CQDs.[4–6]
In order to obtain further insight into the specific optical
properties of MCBF-CQDs, the structure, chemical bonds are
further characterized. The X-ray powder diffraction (XRD) pat-
terns (Figure S9a, Supporting Information) of MCBF-CQDs
show a broad (002) peak centered at around 25°, which con-
firms the graphene structure of MCBF-CQDs. The high degree
of graphitization of MCBF-CQDs is reflected in their Raman
spectrum (Figure S9b, Supporting Information), where the
crystalline G band at 1605 cm−1 is much stronger than the dis-
ordered D band at 1380 cm−1 with a large G to D intensity ratio
(IG/ID) of about 1.8–2.0, indicating the high quality of MCBF-
CQDs, and is consistent with the high degree of crystallinity
of MCBF-CQDs determined by HRTEM (insets of Figure S5,
Supporting Information).[32–34] To the best of our knowledge,
the IG/ID values of MCBF-CQDs are the largest ever reported
for CDs. As shown in Figure S10 (Supporting Information), the
five BF-CQDs exhibit similar Fourier transform infrared (FT-
IR) spectra, revealing the existence of similar chemical compo-
sitions. The strong stretching vibration bands of OH, NH,
and CC are observed at 3435, 3260, and 1616 cm−1, respec-
tively. The strong band at 1530 and 1375 cm−1 are attributed
to CN and CN stretching vibrations, respectively.[35] The
X-ray photoelectron spectroscopy (XPS) surveys further con-
firm the FT-IR data and demonstrate that all five BF-CQDs have
the same elemental composition (i.e., C, N, and O) and
are nitrogen-doped (N-doping level of about 4.14%–6.54%)
(Figure S11, Supporting Information). The deconvoluted high-
resolution XPS spectra for C1s and N1s indicate that they
contain the same chemical bonds (Figure S12, Supporting
Information). The percentage of sp2 hybrid carbon atoms of
MCBF-CQDs calculated from high-resolution XPS spectra is
as high as 89.84%–93.83%, which further demonstrates the
high graphitization of MCBF-CQDs, and is with the large
IG/ID values determined by Raman spectrum. The similar
chemical compositions indicated that the optical properties of
MCBF-CQDs were only associated with different sizes of CQDs
(Figure S5, Supporting Information).
Taken together, it is evident that under the given reaction
conditions the MCBF-CQDs are N doped, highly surface passi-
vated, and have a high degree of crystallinity, yielding the strong
PL emission.[30,32–34,36–38] Taking a step further, we deduce that
the precursor of DAN is crucial for generating the specific
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BF-CQDs. One DAN could be considered as the smallest sp2
domain with a unique amino-substituted rigid carbon skeleton
structure, which concomitantly acts as a building block to form
intact sp2 cluster being N doped in the large rigid π-conjugated
structure and highly surface passivated with amino at edge
sites, which are clearly revealed by FT-IR spectra (Figure S10,
Supporting Information) and deconvoluted high-resolution
XPS spectra (Figure S12, Supporting Information). The dif-
ferent sized BF-CQDs were then achieved through controlled
fusion and carbonization of CA with DAN by controlling the
reaction time, or adding concentrated sulfuric acid as a catalyst
and a dehydrating agent.
The bright bandgap emission of MCBF-CQDs has prompted
us to exploit their applications in LEDs. A conventional simple
structure was used for fabrication of BF-CQDs-based mono-
chrome LEDs from blue to red with the MCBF-CQDs directly
as an active emission layer as shown in Figure 3a. The struc-
ture consists of, from the bottom up, a indium tin oxide (ITO)
glass substrate anode, a poly(3,4-ethylenedioxythiophene):poly
­
(styrenesulfonate) (PEDOT:PSS) hole injection layer (HIL), an
active MCBF-CQDs emission layer, a 1,3,5-tris(N-phenylben-
zimidazol-2-yl) benzene (TPBI) electron transport layer (ETL),
and a Ca/Al double-layered cathode. It should be emphasized
that in our simple device structure, in order to reveal the
origin of EL emission from MCBF-CQDs, no HTL was used.
The energy-level diagram of MCBF-CQDs-based monochrome
LEDs from blue to red was shown in Figure S13 (Supporting
Information). Electrons and holes are injected into the active
BF-CQDs emission layer by an external bias voltage through
ETL (TPBI) and HIL (PEDOT:PSS), respectively. The injected
electrons and holes can undergo radiative recombination in the
BF-CQDs emission layer, giving rise to the EL.
The output EL spectra of MCBF-CQDs-based monochrome
LEDs are presented in Figure 3b–f. They exhibit peak wave-
lengths at 455, 536, 555, 585, and 628 nm, respectively, and are
in good agreement with the PL emission peaks of BF-CQDs
thin films, but red-shifted by about 25–30 nm in wavelength
from the PL measured in the solution due to excessive reso-
nance energy transfer (RET) or direct π–π interactions of close-
packed BF-CQDs in thin films. The photographs in the insets
of Figure 3b–f display the close-up view of the bright, uniform,
and defect-free surface EL emission from blue, green, yellow,
orange, to red emission of BF-CQD-based monochrome LEDs.
The CIE coordinates of the emitted lights of the BF-CQD-based
monochrome LEDs are (0.19, 0.20), (0.31, 0.47), (0.37, 0.52),
(0.46, 0.48), and (0.55, 0.41) as shown in Figure S14 (Supporting
Information), corresponding to blue, green, yellow, orange, and
red emission lights, respectively. The apparently voltage-inde-
pendent emission color of BF-CQD-based monochrome LEDs
(Figure S15, Supporting Information) originated from bandgap
transitions in MCBF-CQDs is of great significance for dis-
play technology. To the best of our knowledge, this is the first
report for fabrication of CQD-based monochrome LEDs with
stable emission color from blue to red with BF-CQDs directly
as an active emission layer by taking advantage of the excellent
bandgap emission.
The typical luminance and current density curves as a func-
tion of applied voltage for MCBF-CQDs-based monochrome
LEDs are shown in Figure S16 (Supporting Information).
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PEDOT:PSS and BF-CQDs emission layer

Figure 3. a) The device structure comprising ITO/PEDOT:PSS (anode), MCBF-CQDs (active
emission layer), TPBi (ETL), and Ca/Al (cathode). The normalized PL spectra and the corre- is even comparable to semiconductor
sponding output EL spectra of b) B-BF-CQDs, c) G-BF-CQDs, d) Y-BF-CQDs, e) O-BF-CQDs,
and f) R-BF-CQDs thin films. The photographs in the insets of (b–f) display the close-up view of
the surface emission from blue, green, yellow, orange, and red emission of monochrome LEDs. using G-BF-CQD-blended PVK as an emis-
The performances of MCBF-CQDs-based monochrome LEDs
are summarized in Table 1. The Von, defined as the bias
voltage applied to LEDs producing a brightness of 0.1 cd m−2,
decreased from 4.7 to 3.7 V for monochrome LEDs from blue
to red, which are much lower than previous reported CD-based
LEDs due to the shallow HOMO energy levels of MCBF-CQDs
and thus resulted in the small hole-injection energy barrier
between ITO/PEDOT:PSS (anode) and BF-CQDs emission
layer (Figure S13, Supporting Information).[20–23] The decreased
Von from B- to R-LEDs could be ascribed to the decreased hole-
injection energy barrier from 0.72 to 0.27 eV between ITO/
Communication
(Figure S13, Supporting Information). The
Lmax and ηc reached about 136 cd m−2 and
0.084 cd A−1 for blue LEDs (B-LEDs), respec-
tively, which are the best performance ever
reported for CD-based monochrome elec-
troluminescent LEDs, and are about six and
four times higher than previous reported
blue LEDs, which used poly-(N,N′-bis(4-
butylphenyl)-N,N′-bis(phenyl) benzidine)
(poly-TPD) as HTL and high excitation-
dependent blue fluorescent CDs as an emis-
sion layer.[20] Other colored monochrome
LEDs were also fabricated under the same
condition with Lmax reaching about 93, 60,
65, and 12 cd m−2 for G-, Y-, O-, and R-LEDs,
respectively. As a benefit of the ultrastable
fluorescence of MCBF-CQDs (Figure S17,
Supporting Information), the monochrome
LEDs all exhibited no temporal degradation
in the emission spectrum under constant
applied bias operation conditions, demon-
strating great potential for practical applica-
tions (Figure S18, Supporting Information).
Moreover, compared with QD-based LEDs
in which the luminance decreased sharply at
high bias voltage, the luminance of BF-CQD-
based monochrome LEDs decreased quite
slowly at high bias voltage, further demon-
strating the substantial stability of BF-CQD-
based monochrome LEDs (Figure S19, Sup-
porting Information).
WLEDs with high performance that
QD-based LEDs have also been fabricated by
sive layer. The typical luminance and current
density curves as a function of applied voltage for the WLEDs
are shown in Figure 4a. The Lmax and ηc reach as high as about
2050 cd m−2 and 1.1 cd A−1 (Figure 4b) with a low Von of about
3.9 V measured for a device with 5.0 wt% G-BF-CQDs as a ben-
efit of the bright bandgap emission of G-BF-CQDs dispersed
in the devices, which can be identified in the EL spectrum of
the WLEDs (Figure 4c). The WLEDs showed broad EL emis-
sion spectrum with two emission peaks centered at about
410 and 517 nm (Figure 4c), which can be assigned to the
emission of PVK (Figure S20, Supporting Information) and
G-BF-CQDs, respectively. The EL emission of WLEDs can be

Table 1. The performances of MCBF-CQDs-based monochrome LEDs from blue to red.

LEDs PLsolution PLfilm EL CIE(X,Y) Von Lmax ηc

[V] [cd m−2] [cd A−1]
B 430 454 455 0.19,0.20 4.7 136 0.084
G 513 534 536 0.31,0.47 4.5 93 0.045
Y 535 552 555 0.37,0.52 4.2 60 0.02
O 565 583 585 0.46,0.48 3.9 65 0.027
R 604 625 628 0.55,0.41 3.7 12 0.0028

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Communi ation
c
Figure 4. a) Luminance–current–voltage (L–I–V) characteristic, b) the current efficiency versus
current density and c) the output EL spectra of WLEDs. The photograph in the inset of (c) dis- (10 mL), the solution was then transferred to a
plays the close-up view of the surface white emission from WLEDs. d) The CIE coordinates of
the white emitted lights from WLEDs.
attributed to the energy transfer from the PVK host to G-BF-
CQDs guest and direct charge injection to G-BF-CQDs. For effi-
cient energy transfer from the host to guest, the absorption of
the guest material must spectrally overlap with the EL emission
of the host. From UV–Vis absorption of G-BF-CQDs and the
EL spectra of PVK (Figure S20, Supporting Information), it is
evident that prerequisite conditions for energy transfer are well
satisfied. The photograph in the insets of Figure 4c displays
the close-up view of the bright, uniform, and defect-free sur-
face white EL emission from WLEDs. The CIE coordinates of
the emitted white lights was realized at (0.30, 0.33), which is
quite close to the pure white light (0.33, 0.33) (Figure 4d).
In summary, we report the first synthesis of MCBF-CQDs
from blue to red with QY up to 75% for blue fluorescence
through a facile solvothermal method. The MCBF-CQDs are N
doped, highly surface passivated, and have a high degree of crys-
tallinity. By taking advantage of the excellent bandgap emission,
monochrome LEDs from blue to red with MCBF-CQDs directly
as an active emission layer are fabricated for the first time. The
Lmax reached about 136 cd m−2 for B-LEDs, which are the best
performance ever reported for CD-based monochrome electro-
luminescent LEDs. The LEDs all show substantial stable EL and
voltage-independent emission color, which is of great signifi-
cance for display and lighting technology. Furthermore, WLEDs
are fabricated with a CIE coordinate realized at (0.30, 0.33).
The Lmax and ηc reaches as high as about 2050 cd m and 1.1 −2
cd A−1 with low Von about 3.9 V even comparable to QDs–LEDs.
This work does serve the purpose of understanding and pro-
viding significant opportunities for further improvements of
CQDs-based electroluminescent LEDs. We expect that further
optimization of the charge injection (holes and electrons), better
controlled device fabrication, as well as material developments
by synthesizing CQDs with the desired charge carrier trans-
port property, will lead to a greatly improved performance for
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CQD-based LEDs. Detailed follow-up work
along this line is under way in our laboratory
and will be reported in due course.
Experimental Section
Synthesis of MCBF-CQDs: The highly tunable
MCBF-CQDs from blue to red were synthesized
by solvothermal treatment of CA and DAN.
For blue and green BF-CQDs: CA (20 mg) and
2,3-diaminonaphthalene (20 mg) were dissolved in
ethanol (10 mL), the solution was then transferred
to a poly(tetrafluoroethylene) (Teflon)-lined autoclave
(25 mL) and heated at 200 °C for 4 and 9 h for the
formation of blue and green BF-CQDs, respectively.
For yellow and orange BF-CQDs: CA (10 mg) and
1,5-diaminonaphthalene (20 mg) were dissolved in
ethanol (10 mL), the solution was then transferred
to a Teflon-lined autoclave (25 mL) and heated at
200 °C for 4 and 9 h for the formation of yellow and
orange BF-CQDs, respectively. For red BF-CQDs:
CA (10 mg) and 1,5-diaminonaphthalene (20 mg)
were dissolved in concentrated sulfuric acid
Teflon-lined autoclave (25 mL) and heated at 200 °C
for 1 h. After the reaction, the reactors were cooled
to room temperature naturally, then the solution
was diluted with deionized water, neutralized by sodium carbonate, and
the supernatant was collected by centrifugation. Finally, the solution was
subjected to dialysis for a week in order to obtain the MCBF-CQDs.
Quantum Yield Measurements: An absolute method, using Varian
FLR025 spectrometer equipped with a 120 mm integrating sphere, was
employed to determine the QY of MCBF-CQDs. We conducted the test
light from FLR025 spectrometer to the sphere. The QY was determined
by the ratio between photons emitted and absorbed by MCBF-CQDs.
The ethanol solution was placed in a UV quarts cuvette with a light path
of 10 mm to measure its QY, while the solvent ethanol filled in the quarts
cuvette was used as a blank sample for the reference measurement.
The spectral correction curve that relates to the sensitivity of the
monochromator, detector, sphere coating, and optics to wavelength was
provided by Edinburgh Instruments.
Characterization Method: Atomic force microscopic images were taken
with MultiMode V SPM (VEECO). A JEOL JEM 2100 transmission electron
microscope (TEM) was used to investigate the morphologies of the
MCBF-CQDs. XRD patterns were carried out by an X-ray diffraction using
Cu-Kα radiation (XRD, PANalytical X’Pert Pro MPD). Absorption spectra
were recorded on UV-2450 spectrophotometry. The fluorescence spectra
of MCBF-CQDs were measured on a PerkinElmer-LS55 luminescence
spectrometer with slit width at 2.5–2.5 nm. The photographs were
taken with a camera (Nikon, D7200) under UV light excited at 365 nm
(UV light: SPECTROLINE, ENF-280C/FBE, 8W). The FT-IR spectra were
measured using a Nicolet 380 spectrograph. XPS was performed with an
ESCALab220i-XL electron spectrometer from VG Scientific using 300 W Al
Kα radiation. The Raman spectrum was measured using laser confocal
micro-Raman Spectroscopy (LabRAM Aramis).
Ultraviolet Photoelectron Spectroscopy Measurement: UPS
measurement was performed with an hv = 21.22 eV, He I source (AXIS
ULTRA DLD, Kratos). The analysis room vacuum was 3.0 × 10−8 Torr,
and the bias voltage for measurement was −9 V. The MCBF-CQDs
thin films were prepared from spin-coating on ITO substrates for UPS
measurement.
Device Fabrication and Characterization: ITO-coated glass substrates
were cleaned ultrasonically in organic solvents (acetone and isopropyl
alcohol), rinsed in deionized water, and then dried in an oven at 150 °C
for 10 min. The substrates were cleaned with a UV-ozone treatment to
enrich the ITO surface with oxygen to increase the ITO work function.
Adv. Mater. 2017, 29, 1604436
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The PEDOT:PSS HIL was spin coated at 2000 rpm for 35 s on the ITO
with a thickness of 40 nm, followed by annealing in an oven at 150 °C
for 15 min. Subsequently, the emissive layer of MCBF-CQDs was spin
coated at 3000 rpm for 45 s over the surface of PEDOT:PSS film from the
ethanol solution and baked on a hot plate at 80 °C for 30 min to form
the active region of the MCBF-CQDs-based monochrome LEDs. Finally,
the substrates were transferred to a vacuum chamber and a 40 nm thick
TPBI ETL was thermally deposited with base pressure of 3 × 10−4 Pa.
After that, a 20 nm Ca and 100 nm thick Al cathode were deposited using
a shadow mask with 2 mm width. The active area of the devices was
thus 4 mm2. The thermal deposition rates for TPBI and Ca/Al are 1, 1,
and 3 Å s−1, respectively. PEDOT:PSS was used as a buffer layer on the
anode mainly to increase the anode work function from 4.7 (ITO) to
5.0 eV and to reduce the surface roughness of the anode to obtain stable
and pinhole free electrical conduction across the device. TPBI was chosen
as the ETL because of its good electron transport capability and its
interfacial phase compatibility with the MCBF-CQDs layer. The thickness
of films was measured using a Dektak XT (Bruker) surface profilometer
and a spectroscopic ellipsometer (Suntech). The devices were measured
without environmental packaging and in atmospheric conditions. The
luminance–current–voltage (L–I–V) characteristics were measured using
a computer-controlled Keithley 236 SMU and Keithley 200 multimeter
coupled with a calibrated Si photodiode. EL spectra were measured by an
Ocean Optics 2000 spectrometer, which couples a linear charge coupled
device (CCD)-array detector ranging from 350 to 1100 nm.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by NSFC of China (21573019), the Major
Research Plan of NSFC (21233003), the Fundamental Research Funds
for the Central Universities.
Received: August 20, 2016
Revised: October 13, 2016
Published online: November 23, 2016
[1] J. Kwak, W. K. Bae, D. Lee, I. Park, J. Lim, M. Park, H. Cho, H. Woo,
D. Y. Yoon, K. Char, Nano Lett. 2012, 12, 2362.
[2] Q. J. Sun, A. Wang, L. S. Li, D. Y. Wang, T. Zhu, J. Xu, C. H. Yang,
Y. F. Li, Nat. Photonics 2007, 1, 717.
[3] X. Bai, G. Caputo, Z. D. Hao, V. T. Freitas, J. H. Zhang, R. L. Longo,
O. L. Malta, R. A. S. Ferreira, N. Pinna, Nat. Commun. 2014, 5,
5702.
[4] C. B. Murray, D. J. Norris, M. G. Bawendi, J. Am. Chem. Soc. 1993,
115, 8706.
[5] V. L. Colvin, M. C. Schlamp, A. P. Alivisatos, Nature 1994, 370, 354.
[6] S. Coe, W. K. Woo, M. G. Bawendi, V. Bulović, Nature 2002, 420,
800.
[7] A. L. Rogach, N. Gaponik, J. M. Lupton, C. Bertoni, D. E. Gallardo,
S. Dunn, N. L. Pira, M. Paderi, P. Repetto, S. G. Romanov, Angew.
Chem. Int. Ed. 2008, 47, 6538.
[8] S. Chanyawadee, R. T. Harley, D. Taylor, M. Henimi, A. S. Susha,
A. L. Rogach, P. G. Lagoudakis, Appl. Phys. Lett. 2009, 94, 233502.
[9] P. Bhattacharya, Z. Mi, Proc. IEEE 2007, 95, 1723.
Adv. Mater. 2017, 29, 1604436 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advmat.de
[10] A. Valizadeh, H. Mikaeili, M. Samiei, S. M. Farkhani, N. Zarghami,
Communication
M. Kouhi, A. Akbarzadeh, S. Davaran, Nanoscale Res. Lett. 2012, 7,
480.
[11] F. L. Yuan, L. Ding, Y. C. Li, X. H. Li, L. Z. Fan, S. X. Zhou,
D. C. Fang, S. H. Yang, Nanoscale 2015, 7, 11727.
[12] Z. T. Fan, Y. C. Li, X. H. Li, L. Z. Fan, S. X. Zhou, D. C. Fang,
S. H. Yang, Carbon 2014, 70, 149.
[13] Y.-P. Sun, B. Zhou, Y. Lin, W. Wang, K. A. S. Fernando, P. Pathak,
M. J. Meziani, B. A. Harruff, X. Wang, H. Wang, P. G. Luo, H. Yang,
M. E. Kose, B. Chen, L. M. Veca, S.-Y. Xie, J. Am. Chem. Soc. 2006,
128, 7756.
[14] M. Zhang, L. L. Bai, W. H. Shang, W. J. Xie, H. Ma, Y. Y. Fu,
D. C. Fang, H. Sun, L. Z. Fan, M. Han, C. M. Liu, S. H. Yang,
J. Mater. Chem. 2012, 22, 7461.
[15] Z. T. Fan, S. H. Li, F. L. Yuan, L. Z. Fan, RSC Adv. 2015, 5, 19773.
[16] F. L. Yuan, S. H. Li, Z. T. Fan, X. Y. Meng, L. Z. Fan, S. H. Yang,
Nano Today 2016, DOI: 10.1016/j.nantod.2016.08.006.
[17] S. Zhu, Q. Meng, L. Wang, J. Zhang, Y. Song, H. Jin, K. Zhang,
H. Sun, H. Wang, B. Yang, Angew. Chem. Int. Ed. 2013, 52, 3953.
[18] F. Wang, S. P. Pang, L. Wang, Q. Li, M. Kreiter, C.Y. Liu, Chem.
Mater. 2010, 22, 4528.
[19] Z. A. Tan, Y. Zhang, C. Xie, H. P. Su, J. Liu, C. F. Zhang, N. Dellas,
S. E. Mohney, Y. Q. Wang, J. K. Wang, J. Xu, Adv. Mater. 2011, 23, 3553.
[20] X. Zhang, Y. Zhang, Y. Wang, S. Kalytchuk, S. V. Kershaw, Y. Wang,
P. Wang, T. Zhang, Y. Zhao, H. Zhang, T. Cui, Y. Wang, J. Zhao,
W. W. Yu, A. L. Rogach, ACS Nano 2013, 7, 11234.
[21] W. Kwon, Y. Kim, C. Lee, M. Lee, H. C. Choi, T. Lee, S. Rhee, Nano
Lett. 2014, 14, 1306.
[22] K. K. Jung, B. Sukang, Y. Yeonjin, J. P. Myung, J. K. Sang,
M. NoSoung, L. Chang-Lyoul, H. H. Byung, H. P. Jong, Sci. Rep.
2015, 5, 11032.
[23] Z. M. Luo, G. Q. Qi, K. Y. Chen, M. Zou, L. H. Y. Wen, X. W. Zhang,
W. Huang, L. H. Wang, Adv. Funct. Mater. 2016, 26, 2739.
[24] H. Tetsuka, R. Asahi, A. Nagoya, K. Okamoto, I. Tajima, R. Ohta,
A. Okamoto, Adv. Mater. 2012, 24, 5333.
[25] Y. Li, Y. Hu, Y. Zhao, G. Shi, L. Deng, Y. Hou, L. Qu, Adv. Mater.
2011, 23, 776.
[26] Y. Li, Y. Zhao, H. H. Cheng, Y. Hu, G. Q. Shi, L. M. Dai, L. T. Qu,
J. Am. Chem. Soc. 2012, 134, 15.
[27] L. Bao, C. Liu, Z. L. Zhang, D. W. Pang, Adv. Mater. 2015, 27, 1663.
[28] H. T. Li, X. D. He, Z. H. Kang, H. Huang, Y. Liu, J. L. Liu, S. Y. Lian,
C. H. A. Tsang, X. B. Yang, S. T. Lee, Angew. Chem. Int. Ed. 2010,
49, 4430.
[29] H. Liu, T. Ye, C. Mao, Angew. Chem. Int. Ed. 2007, 46, 6473.
[30] X. Wang, L. Cao, S. T. Yang, F. Lu, M. J. Meziani, L. Tian, K. W. Sun,
M. A. Bloodgood, Y. P. Sun, Angew. Chem. Int. Ed. 2010, 49, 5310.
[31] L. Wang, Y. Wang, T. Xu, H. Liao, C. Yao, Y. Liu, Z. Li, Z. Chen,
D. Pan, L. Sun, M. Wu, Nat. Commun. 2014, 5, 5357.
[32] X. Y. Tan, Y. C. Li, X. H. Li, S. X. Zhou, L. Z. Fan, S. H. Yang, Chem.
Commun. 2015, 51, 2544.
[33] S. H. Li, Y. C. Li, J. Cao, J. Zhu, L. Z. Fan, X. H. Li, Anal. Chem. 2014,
86, 10201.
[34] R. H. Guo, S. X. Zhou, Y. C. Li, X. H. Li, L. Z. Fan, N. H. Voelcker,
ACS Appl. Mater. Interfaces 2015, 43, 23958.
[35] S. N. Qu, D. Zhou, D. Li, W. Y. Ji, P. T. Jing, D. Han, L. Liu,
H. B. Zeng, D. Z. Shen, Adv. Mater. 2016, 28, 3516.
[36] K. Jiang, S. Sun, L. Zhang, Y. Lu, A. Wu, C. Cai, H. Lin, Angew.
Chem. Int. Ed. 2015, 54, 5360.
[37] Y. Dong, H. Pang, H. B. Yang, C. Guo, J. Shao, Y. Chi, C. M. Li,
T. Yu, Angew. Chem. Int. Ed. 2013, 52, 7800.
[38] W. L. Wei, C. Xu, L. Wu., J. S. Wang, J. S. Ren, X. G. Qu, Sci. Rep.
2014, 4, 3564.
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